WO2016172792A1 - Composés organométalliques utiles pour le dépôt chimique en phase - Google Patents

Composés organométalliques utiles pour le dépôt chimique en phase Download PDF

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WO2016172792A1
WO2016172792A1 PCT/CA2016/050481 CA2016050481W WO2016172792A1 WO 2016172792 A1 WO2016172792 A1 WO 2016172792A1 CA 2016050481 W CA2016050481 W CA 2016050481W WO 2016172792 A1 WO2016172792 A1 WO 2016172792A1
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group
compound
metal
reagent
formula
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PCT/CA2016/050481
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English (en)
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Rajesh Odedra
Cunhai Dong
Shaun CEMBELLA
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Seastar Chemicals Inc.
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Priority to KR1020177031926A priority Critical patent/KR102641862B1/ko
Priority to JP2018507756A priority patent/JP6853814B2/ja
Priority to CN201680029410.6A priority patent/CN107614508B/zh
Priority to US15/569,957 priority patent/US20180155383A1/en
Priority to EP16785706.9A priority patent/EP3288954A4/fr
Publication of WO2016172792A1 publication Critical patent/WO2016172792A1/fr
Priority to US17/010,558 priority patent/US11498938B2/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD

Definitions

  • the invention relates to compounds formed from metal carbonyl complexes with trialkyl silyl, germanyi or stannyl ligands, and to methods of preparing thin films of substantially pure metal, alternatively films of metal alloys, metal oxides, nitrides, phosphides, bo des or sulphides by chemical vapor deposition (CVD) or atomic layer deposition (ALD) using such compounds.
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • Methods of preparing thin films of substantiaily-pure metal alloys, mixed-metal oxides, mixed-metal nitrides, mixed-meta! phosphides, mixed-metal borides or mixed-metal sulphides are also disclosed.
  • Methods of substrate-selective deposition of metal films are also disclosed.
  • organometaliic compounds are used to form thin metal films on a variety of substrates, and a variety of deposition techniques have been employed to do so. These include reactive sputtering, ion-assisted deposition, sol-gel deposition, CVD, and ALD, also known as atomic layer epitaxy.
  • the CVD and ALD processes are increasingly used as they have the advantages of good compositional control, high film uniformity, good control of doping and, significantly, they give excellent confomnal step coverage on highly non-planar microelectronics device geometries.
  • CVD also referred to as metal-organic CVD or MOCVD
  • MOCVD metal-organic CVD
  • MOCVD metal-organic CVD
  • the compounds are passed over a substrate (wafer) within a low pressure or ambient pressure reaction chamber.
  • the compounds react and/or decompose on the substrate surface creating a thin film of deposited material.
  • Volatile by-products are removed by gas flow through the reaction chamber.
  • the deposited film thickness can be difficult to control because it depends on coordination of many parameters such as temperature, pressure, gas flow volumes and uniformity, chemical depletion effects and time.
  • ALD is a common method for the deposition of thin films. It is a self-limiting, sequential, unique film growth technique based on surface reactions that can provide atomic layer-forming control and deposit-conformal thin films of materials provided by compounds onto substrates of varying compositions.
  • the compounds are separated during the reaction. The first compound is passed over the substrate producing a monolayer on the substrate. Any excess unreacted compound is pumped out of the reaction chamber. A second compound is then passed over the substrate and reacts with the first compound, forming a second monolayer of film over the first-formed monolayer of film on the substrate surface. This cycle is repeated to create a film of desired thickness.
  • ALD film growth is seif-iimited and based on surface reactions, creating uniform depositions that can be controlied at the nanometer-thickness scale.
  • This invention is related to compound engineering to meet some of the challenges highlighted above.
  • lower alkyl group refers to linear, branched, or cyclic alkyl groups having from 1 to 8 carbon atoms.
  • linear alkyl groups include, without limitation, methyl groups, ethyl groups, propyl groups, and butyl groups.
  • branched alkyl groups include, without limitation, isopropy! groups and t-butyl groups.
  • cyclic alkyl groups include, without limitation, cyclopropyl groups, cyclopentyl groups, and cyc!ohexy! groups.
  • lower alcohol refers to a primary, secondary or tertiary alcohol having from 1 to 4 carbon atoms.
  • examples of such alcohols include, without limitation, methanol, ethanol, isopropanol and tertiary butanoi.
  • lower alkyl amine refers to a primary or secondary amine having lower a!kyi group(s) each having from 1 to 4 carbon atoms.
  • examples of such amines include, without limitation, methylamine, ethyiamine, di-isopropyiamine and tertiarybutylamine.
  • substituted hydrazine refers to hydrazines having from 1 to 4 substituents which are independently-selected lower alkyi groups, each having from 1 to 4 carbon atoms, or a phenyl group.
  • substituents include, without limitation, ⁇ , ⁇ -dimethyl hydrazine, tertiary-butyl hydrazine, methyi hydrazine and phenyl hydrazine.
  • lower alkyi phosphine refers to a primary or secondary phosphine having lower alkyi group(s) each having from 1 to 4 carbon atoms.
  • examples of such amines include, without limitation, methyl phosphine, dimethylphosphine, ethylphosphine, and tertiary butylphosphine.
  • lower alkyi thiol refers to a primary, secondary or tertiary thiol having from 1 to 4 carbon atoms.
  • examples of such alcohols include, without limitation, methane thiol, ethane thiol, and tertiary-butyl thiol.
  • lower alkyi borane refers to a primary, secondary or tertiary borane, or a precursor thereof, having from 1 to 4 carbon atoms.
  • boranes include, without limitation, methyl borane, ethyl borane, and trimethyl borane.
  • cobalt group metals refers to the elements Co, Rh, and Ir.
  • manganese group metals refers to the elements Mn and Re.
  • chromium group metals refers to the elements Cr, Mo, and W.
  • iron group metals refers to the elements Fe, Ru, and Os.
  • the term "compound” refers to an organometallic molecule, complex and/or compound which is deposited or delivered to or passed over a substrate to form a thin film by a vapor deposition process such as CVD or ALD.
  • metal-containing film refers to a film of substantially pure metal, metal oxide, metal nitride, metal sulphide, metal boride or metal phosphide.
  • vapor deposition process refers to any type of vapor deposition technique such as CVD or ALD.
  • CVD may take the form of conventional (pulsed) CVD, liquid injection CVD or photo-assisted CVD.
  • ALD may take the form of conventional (pulsed) ALD, liquid injection ALD, photo- assisted ALD, plasma-assisted ALD, or plasma-enhanced ALD. Such techniques are well-known in the art.
  • the present invention provides an organometallic compound.
  • the compound corresponds in structure to Formula 1 :
  • R 1 , R 2 and R 3 are independently selected from the group consisting of H, a lower aikyi group and a phenyl group optionally substituted with at least one independently selected lower alkyl group, with the proviso that at least one of R , R 2 and R 3 must be other than H;
  • the cobalt group metals is selected from the group consisting of the cobalt group metals, the iron group metais, the manganese group meta!s, and the chromium group metals;
  • A is selected from the group consisting of Si, Ge, and Sn; and wherein:
  • M is selected from the group consisting of a chromium group metai
  • the compounds are useful in chemical phase deposition processes such as atomic layer deposition (ALD) and chemical vapor deposition (CVD)
  • Methods of deposition of metal-containing films involve the reaction of the compound with at least one co-reagent to generate metal carbonyl hydrides which decompose cleanly and thermally to form substantially-pure metal films.
  • substantially- pure metal oxide, nitride, phosphide, boride or sulphide fiims may be prepared by selection of appropriate co-reagents, as described herein.
  • Methods of selective deposition are also provided, such that metal or metal nitride films are deposited selectively on certain substrates and not on other substrate materials.
  • One such method involves the use of substrate materials having a surface with a strong affinity for the silyl (or germanyl or tin) ligand component of the compound, such that after reaction of the compound with the co-reagent(s) the silyl ligand attaches to the surface having an affinity for Si, inhibiting the deposition of metal on that surface.
  • substrate materials having an affinity include S1O2, SiN, TiN, TaN.
  • An alternative method of selective deposition involves the use of substrate materials having an affinity for CO, such that after reaction of the compound with the co-reagent(s) the metal carbonyl is bound to the surface having such affinity.
  • the metal carbony! is subsequently dissociated thermally, ieaving the metal coating the surface while the CO is removed as gas.
  • substrate materials having an affinity for CO include the nickel group metals Ni, Pd, Pt, cobait group metais Co, Rh, Ir, and iron group metals Fe, Ru, and Os.
  • Fig. 1 shows the vapour pressures of compounds of the invention compared to a compound of the art.
  • Fig. 2 shows the thermal stability of l BuMe 2 SiCo(CO)4.
  • Fig. 3 shows the thermal stability of a compound of the art CCTBA (3,3-Dimethyl-1- butyne)dicobalthexacarbonyl ) .
  • Fig. 4 shows a schematic of a CVD system used for exemplary thin film deposition.
  • Fig. 5 shows the binding energies of 'BuMe2SiCo ⁇ CO)4 on different surfaces.
  • Fig. 6 shows the TGA of EtMe 2 SiCo(CO)4.
  • Fig. 7 shows the vapor pressure of EtMe2SiCo ⁇ CO)4.
  • Fig. 8 shows the NMR spectrum of Et 3 SiCo(CO)4.
  • Fig. 9 shows the NMR spectrum of L Bu e2SiCo ⁇ CO)4.
  • Fig. 10 shows the TGA of l Bu e 2 SiCo(CO)4.
  • Fig. 11 shows the vapour pressure of 'BuMe2SiCo(CO) .
  • Fig. 12 shows the thermal growth rate as a function of temperature for deposition using
  • Fig. 13 shows the NMR of PhMe 2 SiCo ⁇ CO)4.
  • Fig. 14 shows the resistivity of a cobalt film deposited using E BuMe 2 SiCo(CO)4.
  • Fig. 15 shows the growth rate as a function of pressure and the hydrogen to ammonia ratio for deposition using tBuMe2SiCo(CO) .
  • Fig. 16 shows a demonstration of the process of selective deposition using a compound of the invention.
  • An organometallic compound is provided.
  • the compound corresponds in structure to Formula 1 :
  • R 1 , R 2 and R 3 are independently selected from the group consisting of H, a lower a!kyl group and a phenyl group optionally substituted with at least one independently selected lower alkyl group, with the proviso that at least one of R , R 2 and R 3 must be other than H;
  • M is selected from the group consisting of the cobalt group metals, the iron group metals, the manganese group meta!s, and the chromium group metals;
  • A is selected from the group consisting of Si, Ge, and Sn; and wherein:
  • M is selected from the group consisting of a manganese group metal
  • M is selected from the group consisting of a chromium group metal
  • metal carbonyl compounds with tria!kyl sily!, germanyi or stannyl ligands methods of making such compounds and methods of using such compounds, in the presence of appropriate co-reagents, to form substantially-pure metal-containing films, such as, but not limited to, metal, metal phosphide, metal sulphide, metal oxide, metal boride and metal nitride films, are provided.
  • the compound corresponds to Formula 1 wherein M is a cobalt group metal and A is Si.
  • exemplary compounds include Et e 2 SiCo ⁇ CO)4, Et3SiCa(COk Me 2 SiCo(CO)-i and Ph e 2 SiCo ⁇ CO)4.
  • M is an iron group metal
  • A is Si
  • Exemplary compounds include
  • the compound corresponds to Formula 1 wherein M is a manganese group metal and A is Si.
  • Exemplary compounds include Et3SiMn(CO)5-
  • the compound corresponds to Formula 1 wherein M is a chromium group metals and A is Si.
  • Exemplary compounds include (PhMe2Si) 2 W ⁇ CO)4.
  • Embodiments of the invention include those in which R 1 , R 2 and R 3 are independently selected from the group consisting of a lower alkyl group and a phenyl group optionally substituted with at least one independently selected lower alkyl group.
  • Exemplary compounds include those in which R , R 2 and R 3 are independently selected from the group consisting of a lower alkyl group having from 1 to 5 carbon atoms.
  • Other exemplary compounds include those in which at least one of R 1 , R 2 and R 3 is a methyl group.
  • R 1 , R 2 and R 3 are independently selected from the group consisting of a lower alky! group having from 1 to 4 carbon atoms.
  • Other exemplary compounds include those in which at least one of R 1 , R 2 and R 3 is a methyl group
  • R 2 and R 3 are independently selected from the group consisting of a lower alkyl group having from 1 to 4 carbon atoms, two of which are methyl group, the third of which is a lower alkyl group having from 3 to 4 carbon atoms.
  • the compounds of Formula 1 are useful in chemical phase deposition processes such as atomic layer deposition (ALD) and chemical vapor deposition (CVD).
  • ALD atomic layer deposition
  • CVD chemical vapor deposition
  • methods of forming metal-containing films by vapor deposition processes comprise using at least one compound of Formula 1 together with one or more co-reagents, as disclosed herein.
  • Fig. 4 shows a schematic of a CVD system used for exemplary thin film deposition.
  • An inert carrier gas (1 ) such as Ar, is passed through a mass flow controller (2) at a controlled flow rate to bubbler (6), which contains a compound of Formula 1 (7) and carries the vaporized compound of Formula 1 to the reaction chamber (15).
  • a liquid co-reagent (14) is delivered to the reaction chamber in a similar fashion, whereas a gaseous co-reagent is delivered directly to the reaction chamber at a controiled flow rate without going through the bubbler.
  • the bubbler may be heated or cooled to obtain a suitable vapor pressure in the desired range.
  • the temperature of the delivery line is higher than that of the bubbler by about 20 C°, so that the vapor does not condense before reaching reaction chamber.
  • the compound of Formula 1 and the co- reagent are delivered simultaneously.
  • substrate(s) (16) rest on a pre- heated graphite holder (17) at a set temperature controlled by a heater (18) and a thermocouple (19).
  • the pressure in the reaction chamber is controfled by a pressure regulating valve (20), which is connected to a vacuum pump.
  • the delivered compound of Formula 1 and co-reagent react in the reaction chamber, deposit on substrate(s), and so form a thin film.
  • the by-products of the reaction are pumped off under reduced pressure.
  • reaction of a compound of Formula 1 with co-reagents generates meta) carbonyi hydrides, which can decompose cleanly and thermally to form substantially pure metal films, while the volatile carbonyi and hydrolyzed trialkyl silyl ligands evaporate and are removed.
  • co-reagents include, but are not limited to, H2, ammonia, a lower alkyl amine, a lower alcohol, hydrazine and a substituted hydrazine.
  • a seventh embodiment of the invention the reaction of a compound of Formula 1 with co-reagents generates meta! carbonyl oxides, which can decompose cleanly and thermally to form metal oxide films, while the volatile carbonyl and trialkyl siiyl ligands evaporate and are removed.
  • co-reagents include, but are not limited to, hbO, O2, O3, and a lower alcohol.
  • reaction of a compound of Formula 1 with co-reagents generates metal carbonyl amides, which can decompose cieaniy and thermally to form metal nitride films, while the volatile carbonyl and trialkyl siiyl ligands evaporate and are removed.
  • co-reagents include, but are not limited to, ammonia, a lower alkyl amine, a lower alcohol, hydrazine and a substituted hydrazine.
  • reaction of a compound of Formula 1 with co- reagents generates metal carbonyl phosphide, which can decompose cleanly and thermally to form metal phosphide films, while the volatile carbonyl and trialkyl silyl ligands evaporate and are removed.
  • co-reagents include, but are not limited to, Phb and a lower alkyl phosphine.
  • reaction of a compound of Formula 1 with co- reagents generates metal carbonyl sulphide, which can decompose cieaniy and thermally to form metal sulphide films, while the voiatile carbonyl and trialkyl sily ligands evaporate and are removed.
  • co-reagents include, but are not limited to, H 2 S and a lower alkyl thiol.
  • reaction of a compound of Formula 1 with co-reagents generates metal carbonyi borides, which can decompose cleanly and thermally to form metal boride films, whiie the volatile carbonyl and trialkyi silyi ligands evaporate and are removed.
  • co-reagents include, but are not limited to, borane and a lower alkyl borane,
  • the use of more than one compound of Formula 1 , each having a different value of M, in the deposition processes disclosed herein results in the formation of films of substantially-pure metal alloys, mixed-metal oxides, mixed-metal nitrides, mixed-metal phosphides, mixed-metal borides or mixed-metal sulphides, the nature of the film formed being dependent upon the nature of the co-reagent used, as described herein.
  • methods of selective deposition are provided such that metal or metal nitride films are deposited selectively on certain substrates and not on other substrate materials.
  • a thirteenth embodiment of the invention involves the use of substrate materials having a surface with a strong affinity for the silyi (or germanyl or tin, as appropriate) ligand component of the compound of Formula 1 such that, after reaction of the compound of Formula 1 with the co-reagent, the siiyl (or germanyl or tin, as appropriate) ligand attaches to the surface having such affinity, inhibiting the deposition of metai on that surface.
  • Such substrate materials having an affinity include, but are not limited to, S1O2, SiN, TiN, and TaN.
  • a fourteenth embodiment of the invention involves the use of substrate materials having an affinity for CO such that, after reaction of the compound of Formula 1 with the co-reagent, the metal carbonyl is bound to the surface having such affinity.
  • the metal carbonyl is subsequently dissociated thermally, leaving the metal coating the surface whilst the CO is removed as gas.
  • Such substrate materials having an affinity for CO include, but are not limited to, the nickel group metals Ni, Pd, Pt, cobalt group metals Co, Rh, Ir, and iron group metals Fe, Ru, and Os.
  • Fig. 5 shows the binding energies of 'BuMe2SiCo(CO)4 to different surfaces. The more negative the energy, the better binding, meaning that the molecule will bind preferentially to Co or Cu, and thus the deposition will preferentially take place on that surface compared to silicon oxide where the binding is weak.
  • Fig. 12 shows that 'BuMe ⁇ iCoiCOk has good thermal stability up to about 150°C, making it suitable for use in deposition.
  • EtMe2SiCo(CO)i compound in a bubbler was heated at 60 °C, while the NH3 gas was at room temperature.
  • the temperature of the substrate holder was 200 °C.
  • the carrier gas for Co reagent was Ar containing 5% H_.
  • the flow rate of both was ca. 200 seem.
  • the pressure in the reaction chamber was 500 mbar, Substrates used were glass slide, Cu slide and TiN slide. Deposition was carried out for 6 minutes. All substrates were coated with shining Co thin film.
  • Example 9 Deposition of Co thin film using EfaSiCofCOk compound and methanol as co-reagent.
  • Et3SiCo(CO)4 compound in a bubbler was heated at 60 °C, while methanol was cooled to 0 °C.
  • the temperature of the substrate holder was 200 "C.
  • the carrier gas for Co reagent was Ar containing 5% H 2 .
  • the flow rate of both was ca. 200 seem.
  • the pressure in the reaction chamber was 500 mbar.
  • Substrates used were glass slide, Cu slide and TiN slide. Deposition was carried out for 10 minutes. All substrates were coated with shining Co thin film.
  • Example 10 Deposition of Fe thin film using (EfaSibFefCOU compound and NH3 as co-reagent
  • (Et3Si)2Fe ⁇ CO)4 compound in a bubbler was heated at 80 °C, while the NH3 gas was at room temperature.
  • the temperature of the substrate holder was 250 °C.
  • the carrier gas for Co reagent was Ar containing 5% ⁇ 2 .
  • the flow rate of both was ca. 200 seem.
  • the pressure in the reaction chamber was 500 mbar.
  • Substrates used were glass slide, Cu slide and TiN slide. Deposition was carried out for 10 minutes. Fe deposition was confirmed by EDX.
  • Example 1 1 Deposition of CoO thin film using EtMe7SiCo(CO)4 compound and 0? gas as co- reagent.
  • EtMe2SiCo(CO)4 compound in bubbler was heated at 60 °C while the methanol was at room temperature.
  • the temperature of the substrate ho!der was 200 °C.
  • the carrier gas for Co reagent was N 2 .
  • the flow rate of both was ca. 200 seem.
  • the pressure in the reaction chamber was 500 mbar.
  • Substrates used were glass slide, and TiN slide. Deposition was earned out for 6 minutes. All substrates were coated with CoO thin film. During the deposition air was present in the reactor system, resulting in higher oxygen content in the Co film that was deposited. This shows that CoO can be grown with O2 as co-reagent.
  • Example 12 Deposition of Co thin film using ⁇ uMe ⁇ SiCofCOk compound and NH3 ⁇ 4/H? gas mixture as co-reagent.
  • t BuMe 2 SiCo(CO) 4 compound in a bubbler was heated at 40 °C, while the NH3 H2 gas mixture containing 25% H 2 was kept at room temperature.
  • the temperature of the reactor was 200 °C.
  • the carrier gas for Co reagent was l ⁇ b.
  • the flow rate of both was 200 seem.
  • the pressure in the reaction chamber was 100 Torr. Deposition was carried out for 30 minutes. A resistivity of 6.09x10 "5 pOcm was achieved.
  • Fig. 14 shows the conductivity of the cobalt films obtained as a function of hydrogen/ammonia mixture, demonstrating that good quality films with high conductivities can be prepared using a hydrogen/ammonia mixture with greater than about 25% hydrogen.
  • Fig. 15 shows that the growth rate flattens out when about 25-80% hydrogen is used with ammonia, confirming the conductivity data from Fig. 14. Film growth stability is observed,
  • EtMe2SiCo(CO)4 compound in bubbler was heated at 40 °C while the NH3 gas was at room temperature.
  • the temperature of the substrate holder was 200 °C.
  • the carrier gas for Co reagent was N 2 .
  • the flow rate of both was ca. 200 seem.
  • the pressure in the reaction chamber was 90 torr.
  • Initially low pressure CVD was carried out to deposit seed layers of Co metal on Cu Substrate. This was then followed with selective ALD growth of cobait on the seed cobalt layers.
  • there was induction period on the S1O2 surface compared to Cu which allows for selective deposition of cobait on copper as compared to silicon oxide, as shown in Fig. 16.
  • FIG. 4 The following reference characters are used in Fig. 4: 1 Inert carrier gas input; 2 Mass flow controller; 3 Valve controliing direct input of inert carrier gas to reaction chamber; 4 Valve controlling input of inert carrier gas to bubbler; 5 Vaive controlling input of inert carrier gas containing vaporized precursor to reaction chamber; 6 Bubbler containing compound; 7 Compound; 8 Input of gaseous co-reagent or inert earner gas for liquid co-reagent; 9 Mass flow controller; 10 Valve controlling direct input of gaseous co-reagent or inert carrier gas; 11 Valve controlling input of inert carrier gas to bubbler; 12 Vaive controlling input of inert carrier gas containing vaporized co- reagent to reaction chamber; 13 Bubbler containing co-reagent; 14 Liquid co-reagent; 15 Quartz tube wall of reaction chamber; 16 Substrate; 17 Graphite substrate holder with heater and thermocouple; 18 Heater; 19 Thermocouple; 20 Pressure regulating valve to vacuum pump controlling gas

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  • General Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
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Abstract

L'invention concerne des composés organométalliques utiles dans des procédés de dépôt chimique en phase comme le dépôt de couche atomique (ALD) et le dépôt chimique en phase vapeur (CVD). Les composés correspondent en structure à la formule 1 : [{R1R2R3 (A))x-M(CO)y]z dans laquelle R1, R2 et R3 sont indépendamment choisis dans le groupe constitué de H, un groupe alkyle inférieur et un groupe phényle facultativement remplacé par au moins un groupe alkyle inférieur choisi indépendamment, à condition qu'au moins l'un de R1, R2 et R3 soit obligatoirement différent de H ; M est choisi dans le groupe constitué du cobalt, de métaux du groupe du cobalt, de métaux du groupe du fer, de métaux du groupe du manganèse et de métaux du groupe du chrome ; A est choisi dans le groupe constitué de Si, Ge et Sn ; et dans laquelle : x = 1, y = 4 et z = 1 lorsque M est choisi dans le groupe constitué d'un métal du groupe du cobalt, x = 1, y = 5 et z = 1 lorsque M est choisi dans le groupe constitué d'un métal du groupe du manganèse, x = 2, y = 4 et z = 1 lorsque M est choisi dans le groupe constitué d'un métal du groupe du chrome, et x = 2, y = 4 et z = 1 ou, en variante, x = 1, y = 4 et z = 2 lorsque M est choisi dans le groupe constitué d'un métal du groupe du fer. L'invention concerne également des procédés de dépôt qui impliquent la réaction d'au moins un des composés de l'invention, en présence de co-réactifs, pour produire des hydrures de métal carbonyle qui peuvent se décomposer proprement et thermiquement pour former des film métalliques sensiblement purs, des films d'oxyde métallique, des films de nitrure de métal, des films de phosphure de métal, des films de borure métallique ou des films de sulfure de métal. L'invention concerne des procédés de dépôt sélectif, de telle sorte que des films métalliques ou contenant du métal sont déposés de manière sélective sur certains substrats et pas sur d'autres matériaux de substrat.
PCT/CA2016/050481 2015-04-30 2016-04-25 Composés organométalliques utiles pour le dépôt chimique en phase WO2016172792A1 (fr)

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KR1020177031926A KR102641862B1 (ko) 2015-04-30 2016-04-25 화학 상 증착용 유기금속 화합물
JP2018507756A JP6853814B2 (ja) 2015-04-30 2016-04-25 化学相堆積に有用な有機金属化合物
CN201680029410.6A CN107614508B (zh) 2015-04-30 2016-04-25 用于化学相沉积的有机金属化合物
US15/569,957 US20180155383A1 (en) 2015-04-30 2016-04-25 Organometallic compounds useful for chemical phase deposition
EP16785706.9A EP3288954A4 (fr) 2015-04-30 2016-04-25 Composés organométalliques utiles pour le dépôt chimique en phase
US17/010,558 US11498938B2 (en) 2015-04-30 2020-09-02 Organometallic compounds useful for chemical phase deposition

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TWI790943B (zh) * 2022-03-11 2023-01-21 漢民科技股份有限公司 化學氣相沉積系統與方法

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Publication number Priority date Publication date Assignee Title
WO2019030117A1 (fr) 2017-08-09 2019-02-14 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Matériau de formation de co-film contenant du ge, co-film contenant du ge et procédé de formation de film correspondant
JP2019031477A (ja) * 2017-08-09 2019-02-28 レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード Ｇｅ含有Ｃｏ膜形成材料、Ｇｅ含有Ｃｏ膜およびその成膜方法
US11205573B2 (en) 2017-08-09 2021-12-21 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Ge-containing Co-film forming material, Ge-containing Co film and film forming method thereof
JP7143124B2 (ja) 2017-08-09 2022-09-28 レール・リキード－ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード Ｇｅ含有Ｃｏ膜形成材料、Ｇｅ含有Ｃｏ膜およびその成膜方法

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US20200399300A1 (en) 2020-12-24
KR102641862B1 (ko) 2024-02-27
CN107614508B (zh) 2021-04-27
TW201704511A (zh) 2017-02-01
US11498938B2 (en) 2022-11-15
JP2018515694A (ja) 2018-06-14
JP6853814B2 (ja) 2021-03-31
EP3288954A4 (fr) 2018-12-12
US20180155383A1 (en) 2018-06-07
EP3288954A1 (fr) 2018-03-07
KR20180004131A (ko) 2018-01-10
TWI734684B (zh) 2021-08-01

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